New imides, their manufacture and their use as microbiocides

ABSTRACT

New imides of the formula   WHEREIN Z represents hydrogen or methyl, X represents oxygen, sulphur or the group NR3, in which R3 represents hydrogen or methyl, R1 represents hydrogen, chlorine, bromine or trifluoromethyl, and R2 represents hydrogen, halogen, methyl or trifluoromethyl, a process for their manufacture and their use for combating representatives of the division Tallophyta are disclosed.

United States Patent [191 Moser et al.

[4 1 July 8,1975

[ IMIDES, THEIR MANUFACTURE AND THEIR USE AS MICROBIOCIDES [75] lnventors: Hans Moser, Magden/AG; Elmar Sturm, Aesch; Raphael Menasse, Basel, all of Switzerland [73] Assignee: Ciba-Geig y Corporation, Ardsley,

22 Filed: Jan. 8, 11973 21 App]. No.: 321,624

[30] Foreign Application Priority Data Jan. 12, 1972 Switzerland 438/72 Dec. 4, 1972 Switzerland 17626/72 [52] US. Cl. 260/3265 S; 260/3765 FM; 424/274 [51] lint. Cl (107d 27/18 [58] Field of Search 260/3265 FM, 326.5 S

[56] References Cited UNlTED STATES PATENTS 2,962,504 11/1960 Walker et a1. 260/3265 FOREIGN PATENTS OR APPLICATIONS 1,145,583 3/1969 United Kingdom 260/3265 Primary Examiner-Joseph A. Narcavage Attorney, Agent, or Firml-larry Falber; Frederick H. Rabin [57] AESTRA CT New imides of the formula wherein Z represents hydrogen or methyl, X represents oxygen, sulphur or the group NR in which R represents hydrogen or methyl, R represents hydrogen, chlorine, bromine or trifluoromethyl, and R represents hydrogen, halogen, methyl or trifluoromethyl, a process for their manufacture and their use for combating representatives of the division Tallophyta are disclosed.

6 Claims, No Drawings NEW IMTDES, THEIR MANUFACTURE AND T illlETlR USE AS MTRBTOTDES The present invention relates to new dichloromaleic imides, their manufacture and use in pest control.

The dichloromaleic imides have the formula wherein Z represents hydrogen or methyl, X represents oxygen, sulphur or the group NR in which R represents hydrogen or methyl, R represents hydrogen, chlorine, bromine or trifluoromethyl, and R represents hydrogen, halogen, methyl or trifluoromethyl.

By halogen is meant fluorine, chlorine, bromine or iodine, but in particular chlorine or bromine.

Preferred compounds on account of their action are those of the formula The active substances of the formula I can be manufactured by known methods which are described in the literature, for example by reacting the compound of the formula with a compound of the formula The starting materials of the formulae Ill and IV are known compounds, the processes for the manufacture of which are described in the literature.

The compounds of the formula l have a broad biocidal activity spectrum and can be used for combating various plant and animal pests. The activity of these compounds is good against representatives of the division Thallophyta, chiefly against plant pathogenic fungi, especially leaf fungi, for example on cereals, rice, vegetables, vines, fruit and other cultures, from the series Oomycetes, Moniliales, Uredinales, Erysiphales, Sphaeropsidales, e.g. Botrytz's cinerea, Piricularia oryzae, Poa'osphaera leutoricha, Uromyces appendiculatus, Plasmopara viticola, Septoria agricola, Puccinia triticina.

The active substances according to the invention are also active against fungi which attack the plants from the soil and partially cause tracheomycosis, and also those which damage seeds present in the soil.

The fungicidal action of the compounds of the formula l can be substantially broadened and adapted to the given circumstances by the addition of other fungicides. The following compounds, for example, are suitable additives:

elementary sulphur ammonium polysulphide and metal polysulphides boric acid and borates nickel sulphate potassium chromate copper (I) oxide (KUlPFEROXlD) Bordeaux broth and further inorganic and organic copper salts bis-(tri-n-butyl tin)oxide triphenyl tin hydroxide (FENTINHYDROXID) triphenyl tin acetate (FENTlNACETAT) and further organic tin compounds methyl mercury-8-hydroxyquinolate (Ortho LM) N-(methyl mercury)-l,4,5,6,7,7-

hexachlorobiycyclo[2.2. 1 ]hept-5-ene-2,3- dicarboximide N-(ethylmercury)-1 ,4,5,6,7,7,-

hexachlorobicyclo]2,2.l ]hept--ene-2,3- dicarboximide N-(ethyl mercury)-p-toluenesulphonic anilide phenyl mercury acetate (PMA) phenyl mercury urea mixture of ethyl mercury-2,3-dihydroxypropyl mercaptide and ethyl mercury acetate and further inorganic and organic mercury compounds 0,0-diethyl-phthalimidiphosphonothioate 5-amino-bis-(dimethylamido )phosphinyl-3-phenyl- 1,2,4-triazole (TRlAMlPl-lOS) 5-methylamino-bis-(dimethylamido )-phosphinyl-3- phenyl-1,2,4-triazole 0,0-diethyl-0-2-pyrazinyl-phosphorus thioate O-ethyl-S,S-diphenyl-dithiolphosphate O-ethyl-S-benzyl-phenyldithiophosphonate 0,0-diisopropyl-S-benzyl-phenyldithiophosphonate 0,0-diethyl-S-benzyl-thiophosphate O-butyl-S-ethyl-Sbenzyl-dithiolphosphate O-pentachlorophenyl-bis-( dimethylamido)- phosphate O-ethyl-S-benzyl-phenyl-phosphonate diethylamido-benzenethiophosphonic-Z-methylimidazolide methylbromide methyl isocyanate 1,3-dichloropropene and related halogenated C and C hydrocarbons l-chloro-2-nitro-propane 2-chlorol-nitropropane dichlorotetrafluoroacetone sorbic acid and its potassium salts dodecylguanidine acetate (dodine) dodecylguanidine phthalate acetylene dicarboxylic diamide 1,2-dicyano-l ,2-dichloroethylene l ,2-dichloro-1-(methylsulphonyl)ethylene l ,Z-dichlorol butylsulphonyl )ethylene transl ,2-bis-(n-propylsulphonyl)ethylene bis-( 1 ,2-trichloroethyl)sulphoxide bis-(n-propyl-chlorodifluoromethylthio)-sulphone diamide p-dichlorobenzene hexachlorobenzene (HCB) 1 ,2,4-tetrachloro-4-nitrobenzene(TECNACEN) pentachloronitrobenzene (QUlNTAZEN) isomer mixture of l,3,4-trichloro-2,6-dinitrobenzene diphenylrnethane 2,2 '-dihydr'oxy-5 ,5 -dichloro-diphenylsulphide 2,2-dihydroxy-3 ,3 ',5,5 -tetrachlorodiphenylsulphide disodium-2,2 '-dihydroxy-3 ,3 ,5 ,5 -tetrachlorodiphenylsulphide 4-chloro-o-phenylphenol l,4-dichloro-2,S-dimethoxybenzene (CHLORNEB) salicylanilide l ,2-bis-( 3-methoxycarbonyl-2-thiourea)-benzene 1 ,2-bis-( 3-ethoxycarbonyl-2-thiourea)-benzene (3 ,5-dimethyl-4-chlorophenoxy )-ethanol 1 ,4-dichloro-2,S-dimethoxybenzehe 2,4,5-trichlorophenylsulphonylmethylthiocyanate phenylmercapto-methanesulphonamide 2-( l-methyl-n-propyl )-4,6-dinitrophenyl-2- methylcrotonate (BlNAPACRYL) 2-( l-methyl-n-propyl)4,6-dinitrophenylisopropylcarbonate (DINOEUTON) v 2-( l-methyl-n-heptyl )-4,6-diniitrophenylcrotonate (DINOCAP) methyl-2,6-dinitro-4-( l-ethyl-hexyl)phenylcarbonate methyl-2,6-dinitro-4-( l-propyl-pentyl )phenylcarbonate (DINOCTON) 4-nonyl-2,6-dinitro-phenylbutyrate S-methyl-2-( l-methyl-n-heptyl )-4,6-

dinitrophenylthiocarbonate l-( 3 ,4-dichloroanilino )-l -formylamino-2,2,2-

trichloroethane 2,6-dichloro-4-nitroaniline (DICHLORAN) 2-cyanoethyl-N-phenylcarbamate propynyl-N-phenylcarbamate 2-methyl-benzoic anilide 2-iodo-benzoic anilide 2-chloro-benzoic anilide 2,3,5,6-tetrachloro-benzoquinone (1,4) (CHLOR- ANIL) 2,3-dichloro-naphthoquinone( l ,4) (DICHLON) Z-amino-3-chloro-naphthoquinone 1.4)

2-chloro-3-acetamino-naphthoquinone( 1,4)

4-methyl-2,3 ,5 1 O-tetrahydro-3 ,5 l O-trioXo-4H4-H- naphtho(2,3 ,-b)-1 ,4-thiazine quinoximbenzoylhydrazone (BENQUINOX) N-(trichloromethylthio )phthalimide (FOLPET) N-( trichloromethylthio )cyclohex-4-enel ,2-

dicarboximide (CAPTAN) N-( 1 ,1,2,2-tetrachloroethylthio)cyclohex-4-ene-1,2-

- dicarboximide (CAPTAFOL) N-( l,l,2,2-tetrachloroethylthio)cyclohex-4-ene-1,2-

dicarboximide N-dichlorofluoromethylthio-NN-dimethyl-N'- phenylsulphamide (DICHLOFLUANIDE) S-( 2-pyridyll -oxide )-S -trichloromethyl-disulphide:

hydrochloride sodium-N-methyl-dithiocarbamate (METHAM) sodium-N,N-didmethyl-dithiocarbamate (DDC) zinc-N,N-dimethyl-dithiocarbamate (ZlRAM) iron-N,N-dimethyl-dithiocarbamate (FERBAM) disodium-ethylene-l ,2-bis-dithiocarbamate (NABAM) zinc-ethylene-1,2-bis-dithiocarbamate (ZINEB) manganese (ID-ethylene 1,2-bis-dithiocarbamate (MANEB) zinc-propylene-l ,2-bis-dithiocarbamate (MEZINEB) (PROPINEB) p-nonylphenoxypolyethyleneoxyethanol iodine complex (a-nitromethyl )--chlorobenzythioethylamine hydrochloride v 3-(p.-t.-butyl-phenylsulphonyl)-acrylonitrile 5 octachlorocyclohexenone pentachlorobenzyl alcohol pentachlorobenzyl acetate pentachlorobenzaldehyde cyanohydrin Z-norcamphane-methanol 2,6-bis-(dimethylaminoethyl)-cyclohexanone decachloro-octahydrol ,3 ,4-metheno-2H-cyclobuta [cd]pentalen-2-one l-( 3-chloroallyl)-3,5 ,7-triazal -azonia-admantane chloride.

The compounds of the formula I can be used in plant protection as pure active substance or together with suitable carriers and/or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally usedin formulation technology, for example, natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilisers.

The agents according to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula ll with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may be available and can be used in the following forms:

Solid forms:

Dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous granules. Liquid forms:

a. active substances which are dispersible in water:

wettable powders, pasts, emulsions;

b. solutions.

\ To manufacture solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaccous, earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers, for exampleammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used alone or in admixture with one anotzer.

Granules can be very easily manufactured by dissolving an active substance of the formula I in an. organic solvent and applying the resulting solution to a granulated material, for example attapulgite, SiO granicalcium, bentonite etc. and then evaporating the solvent.

Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/formaldehyde; dicyan- 60 diamide/formaldehyde; melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio, with the active sub.- stances, for example in the form of their solutions (in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 g/litre to 600 g/litre can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants.

It is also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently comminuting the product.

To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionic and cationic surface active substances, which for example improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivates (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of 'monoalkyl and dialkyl phenols having five to 15 ethylene oxide radicals per molecule and eight to nine carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having five to 20 ethylene oxide radicals per molecule and eight to 18 carbon atoms in the fatty a1- cohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e., wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substance and anti-foam agents and, optionally, solvents.

Wettable powder and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers in suitable apparatur until homogeneity is attained. Carriers are, for example, those mentioned for the solid forms of appliaction. In some cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulfonic acid, in addition, alkylaryl sulfonates, alkali and alkaline earth metal salts of dibutyl naphthalene sulfonic acid, fatty alcohol sulfates such as salts of sulfated hexadecanlos, heptadecanols, octadecanols, and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salt of oleoyl methyl tauride, ditertiary acetylene glycols, dialkal dilauryl ammonium chloride and fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones.

,The active substances are mixed, ground, sieved and 'strained with the additives mentioned above that, in

such as those cited above, organic solvents and water are used. Examples of suitable solvents are the following: alcohols, benzene, xylene, toluene, dimethyl sulfoxide, and mineral oil fractions boiling between 120 and 350C. The solvents must be practically odorless, not phytotoxic, inert to the active substances and not readely inflammable.

Furthermore, the agents according to the invention can be applied in the form of solutions. For this purpose the active substance or several active substances of the general formula l are dissolved, in suitable organic solvents, mixtures of solvents or in water. Ali phatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, and mineral oils alone or mixed with each other, can be used as organic solvents.

The content of active substance in the above described agents is between 0.1% to 95%, in which connection it should be mentioned that in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5% or even pure active substance.

The active substances of the formula 1 can, for example, be formulated as follows:

Dusts The following substances are used to manufacture a a and b a 2% dust.

u 5 parts of active substance 95 parts of talcum b 2 parts of active substance 1 part of higly disperse silica 97 parts of talcum.

The active substances are mixed with the carriers and ground. Granules The following substances are used to produce 5% granules:

5 parts of active substance,

(1.25 parts of epichlorohydrin,

0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.2-0.8 mm).

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on to kaolin, and the acetone subsequently evaporated in vacuo.

Wettable powder The following constituents are used for the preparation ofa a 40%, b and c a 25%, and d a 10% Wettable powder:

parts of active substance,

5 parts of sodium lignin sulphonate,

1 part of sodium dibutylnaphthalene sulphonate,

parts of silica acid.

parts of active substance,

5 parts of calcium lignin sulphouate .9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silica acid,.

-Continued 19.5 parts of Champagne chalk, 28.1 parts of kaolin. c 25 parts of active substance,

2.5 parts of isooctylphenoxy-polyoxyethyleneethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 8.3 parts of sodium aluminium silicate, parts of kieselguhr, 46 parts of kaolin, d 10 parts of active substance,

3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid/ formaldehyde condensate, 82 parts of kaolin.

The active substances are intimately mixed, in suitable mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable power are obtained which can be diluted with water to give suspensions of any desired concentration. Emulsifiable concentrates The following substances are used to produce a a 10% and b a 25% emulsifiable concentrate:

a 10 parts of active substance,

3.4 parts of epoxidised vegetable oil,

13.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt,

40 parts of dimethylformamide,

43.2 parts of xylene.

b 25 parts of active substance,

2.5 parts of epoxidised vegetable oil, 10 parts of an alkylarylsulphonate/fatty alcoholpolyglycol ether mixture, 5 parts of dimethylformamide,

parts of xylene.

From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concen tration.

Spray The following constituents are used to prepare a 5% spray:

5 parts of active substance, 1 part of epichlorohydrin, 94 parts of benzine (boiling limits 160 C).

EXAMPLE 1 Action against Botrytis cinerea 0n Vicia faba Fully developed, uniformly large leaves of Vicia faba,

which have been sprayed dripping wet from a spraying 55 device with a broth (0.1% content of active substance) prepared from an active substance formulated as a 10% wettable powder, were placed three at a time in Petri dishes lined with filter paper. When the leaves were dry again, they were infected with a freshly prepared, standardised spore suspension of the fungus (concentration: 100'000 spores/ml) and kept for 48 hours in a .humid atmosphere at 20C. After this time, the leaves displayed black, initially dot-shaped specks which rapidly spread. The number and size of the infected areas served as a yardstick for determining the effectiveness of the test substance.

The compounds of the formula I showed good action in the above test against Botrytis cinerea.

EXAMPLE 3 Action against Uromyces appendiculates on Phaseolus vulgaris at 20-22c.

The'number and size ofthe rust pustules served as a yardstick for assessing the effectiveness of the active substances The compounds according to Example 1 showed good action in the above test against Uromyces appendiculatus.

T13 EXAMPLE 4- Action against Poa'osphaera leucotricha (Ell. er Ev.) Salm. on young apple trees Apple tree cuttings of the type MM lll were reared in a greenhouse at 20C and 90% relative humidity throughout the duration of the test. When three to four leaves had formed on each of the developing lateral shoots, these leaves were sprayed dripping wet with a broth (0.1% content of active substance) prepared from the active substance formulated as 10% wettable powder. After the coating layer had dried, the leaves were uniformly sprayed on the topside with a spore suspension of the fungus.

The trees were sprayed again with the above described active substance preparation 7 14- days after the first treatment. The test was evaluated 12 days after the final treatment The number and size of the infected areas served as a yardstick for evaluating the effectiveness of the test substance.

The compounds according to Example 1 showed good action in the above test against Podosphaera leuctricha(Ell.et Ev.)Salm.

EXAMPLE Action against Plasmopara viticola (Bert. et Curt.) (Berl. et De Toni) on vines Vine cuttings of the variety Chasselas were reared in a greenhouse. Three plants in the l0-leaf stage were sprayed dripping wet with a broth (0.1% active substance content) prepared from the active substance formulated as a wettable powder. After the coating layer had dried, the plants were uniformly infected on the underside of the leaves with the spore suspension of the fungus. The plants were subsequently kept for 8 days in a humid chamber, after which time the symtoms of disease became visible on the control plants. The number and size of the infected areas served as a yardstick for evaluating the effectiveness of the active substance.

The compounds according to Example 1 showed good action in the above test against Plasmopara viticola (Bert.et Curt.)(Berl. et De Toni).

EXAMPLE 6 Action against Septoria agricola Spegazzini on celery plants Celery plants of the variety Challon were reared in a greenhouse. Fifteen centimetre high plants were each sprayed dripping wet with a broth (0.1% content of active substance) prepared from the active substance formulated as 10% wettable powder. After the coating layer had dried, the plants were infected with a spore suspension of the fungus. Symptoms of disease occured after 2 days in a humid chamber and 12 days at 22C and 90% relative humidity in a greenhouse. The number and size of the infected areas served as a yardstick for evaluating the effectiveness of the test substance.

The compounds according to Example 1 showed good action in the above test against Septoria agricola Spegazzini.

EXAMPLE 7 Action against Puccinia triticina Erites on Triticum in a greenhouse at 20C young wheat plants app. 10 cm in length were sprayed dripping wet with a broth (0.1% content of active substance) prepared from the active substance formulated as a 10% wettable powder. When the coating layer had dried, the plants were uniforrnly infected with a uredospore suspension of the fungus. Evaluation took place after 5 days in a humid chamber and 12 days in a greenhouse at 2 022C and normal relative humidity. The number and size of the infected areas served as a yardstick for evaluating the effectiveness of the test substance.

The compounds according to Example 1 showed good action in the above test against Puccinia triticina Eritess.

EXAMPLE 8 Action against Piricularia Oryzae Bri. er Cav. on rice Rice plants were reared in a greenhouse and sprayed once prophylactically with an aqueous spray both containing 0.1% active substance. Two days later, the 10 treated plants were infected with exospores of Piricu- [aria oryzae Bri. et Cav. and examined for attack by fungus after 5 days incubation in a humid chamber.

The compounds according to Example 1 showed good action in the above test against Piricularia oryzae.

We claim:

ll. Compounds of the formula wherein Z represents hydrogen or methyl, X represents oxygen, sulphur or the group NR in which R represents hydrogen or methyl, R represents hydrogen, chlorine, bromine or trifluoromethyl, and R represents hydrogen, halogen, methyl or trifluoromethyl.

2. The compound according to claim ll of the formula 15 16 3. The compound according to claim 1 of th formula 5. The compound according to claim [of the formula 0 l ll c1 c 5 c I n-cn -cu -s cu v l f C I C l I; Cit 1 10 J I 6. The compound according to claim 1 of the formula 4. The compound according to claim 1 of the formula 5 

1. COMPOUND OF THE FORMULA
 2. The compound according to claim 1 of the formula
 3. The compound according to claim 1 of the formula
 4. The compound according to claim 1 of the formula
 5. The compound according to claim 1 of the formula
 6. The compound according to claim 1 of the formula 